New anthraquinone vat dyestuffs



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* fl ed S at 8 Max Staeuble, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss firm 7 No Drawing. Application July 13, 1953,

Serial No. 367,719 V y o Claims priority, applicationswitzerland July 23, 1952 7 Claims. (Cl. 260247.1)

This invention provides new anthraquinone vat dyestuifs which, like the dyestutt' of the constitution H C) HNOC-C\ /C-SOr-N\ S CH: 01

r a YEN-00G, correspond to the general formula (2) v p v HC0H.

- t t t") HNOC -S02X S halogen halogen Hl I OCRi in-which R1 represents a radical of the benzene series and X stands for one of the radicals s-onzoni wherein m and it each represents a whole number of at the most 3.

The invention also includes a process for making these new dyestutfs, wherein the amino group in the 1-position of a 1-arnino-4-acylamino-6:7-dihalogen-anthraquinone is acylated, and the starting materials are so chosen that one of the acyl radicals in the vat dyestutf so obtained 1s a benzoyl radical, which may contain further substituents, and the other acyl radical corresponds to the formula (3) HC-CH wherein X has the above-mentioned meaning.

The l-amino-4-acylamino 6:7 dihalogen anthraquinones used as starting materials in the present process may contain two identical halogen atoms in the 6- and 7-positions, for example, 2 chlorine atoms or 2 bromine atoms, or may contain in those positions two different halogen atoms, for example, a chlorine atom and a fluorine, bromine or iodine atom.

2,749,341 Patented June 5,

" groups, or a phenyl radical bound directly: to the ,benzoyl radical. However, the benzoyl radical i s adyan tageously free from sulfone groups-,and.sulfonamide groups, or, stated more generally, the starting materials are advantageously so chosen that the resulting dyestutf contains in the acyl radicals as the sole sulfur-containing substituent the sulfonicv acid, amide group present in the radical of the Formula 3. .7 1

The acyl radicals of ,the are derived from thiophene-Z-carboxylic acid-S-stilfonic acid, and advantageously contain alkyl groups of lowmolecular weight,

for example, methyl, ethyl,.n-propyl. orisopropyl groups. The two alkyl groups may ,.be..c'onnected together, .for example at their end carbon atoms, directly or through a hetero-atom, so that together withuthe nitrogen atom of the sulfonic acid amide groupthey form acfurth'er heterocyclic ring, for example, a morpholine or piperidine ring. t

The 1-amino-4-acylamino-6 7- dihalogenanthraquinones used as starting materials may, as will beapperent from the foregoing statements, contain as the acyl radical either a benzoyl radical or a radical of the.Formula 3. They can be made by methods in themselves. known, for example, by monoacylating ,1:4-diamino-6z7-dihalogenanthraquinones ,or by the reduction of 1-nitro-4-acylamino-6:7-dihalogenanthraquinones, which latter can be made by acylating l-nitro-4-amino-6:7-dihalogen anthraquinones. 4

The further acylation of vthe resulting 1-amino-4- acylamino-6z7-dihalogen anthraquinones with the benzoylating agents or acylating agents capable of introducing the radical of the Formula 3 can be carried out, also by methods in themselves known, and advantageously with-the use of the corresponding carboxylic acid halides, especially the chlorides, It is of advantage to carry out the acylation in a high boiling solvent such as dichlorobenzene, or nitrobenzene at a raised, temperature, for .example, atemperature above 100 ,,C., if, desired withtthe addition of an acid-binding agent and/or a catalytically active agent such as pyridine, diethylamine or-,sodium carbonatei The new dyestuffs of thisinvention, which correspond to; the above Formula 2, can be used as pigment dyestuffs and also for dyeing or printing a very wide variety of-;materi als, especially cellulose-containing materials suchas cotton, linen or artificial silk :or staple fibers of regenerated cellulose. If desired, they maybe used in the form of their leuco-ester salts prepared in the usual manner and applied by the methods known for this class of dyestuffs. The dyeings are usually distinguished by their pure tint andgood propertiespf fastness The following examples illustrate the invention, the parts and percentages being by weightunless ptherwise stated and the relationship of parts'by weight to parts by volume being the same as that of the kilogram to the I liter:

Example 1 l ii HN-OC-O This dycstuff dyes cotton from an olive-green hydrosulfite vat fast pure reddish violet tints.

Example 2 1.3 parts of thiophene-Z-carboxylic acid-S-sulfonic acid dimethylamide are stirred for /2 hour at 90 C. with 1.2 parts of thionyl chloride in 30 parts of dry nitrobenzene, and then condensed with 2.3 parts of l-benzoylamino-4-amino-6-chloro-7-bromanthraquinone at 125- 130 C. for 2 hours. After cooling the mixture, the dyestuff which has crystallized out is filtered off, washed with alcohol, and dried in vacuo at 110 C. There are obtained about 3 parts of the dyestuff, which is obtained by recrystallization from nitrobenzene in the form of violet-red lamellae. This dyestutf dyes cotton from an olive green hydrosulfite vat fast pure violet-red tints. This dyestuif, which contains one atom of chlorine and one atom of bromine per molecule, dyes a somewhat more bluish tint than the dyestuff described in Example 1 which contains a chlorine atom in each of the 6- and 7-positions of the anthraquinone nucleus.

1 benzoylamino 4 amino-6-chloro-7-bromanthraquinone can be prepared from 2-chl0ro3bromanthraquinone (obtained from 2-amino-3-bromanthraquinone by diazotization followed by reaction with cuprous chloride) by nitration, reduction, conversion of the amine so obtained into its oxamic acid, further nitration, splitting oil of the oxalic acid radical, benzoylation and reduction.

Example 3 It dyes cotton from an olive-green hydrosulfite vat fast wine red tints.

By using, instead of 1.5 parts of thiophene-Z-carboxylic acid--sulfonic acid diethylamide, 1.55 parts of thiophene-2-carboxylic acid-5-sulfonic acid piperidine (obtained from thiophene-Z-carboxylic acid-S-sulfonic acid chloride and piperidine) there are obtained about 2.3 parts of the dyestutf of the formula By using, instead of 1.5 parts of thiophene-Z-carboxylic acid-S-sulfonic acid diethylamide, 1.55 parts of thiophene-Z-carboxylic acid-S-sulfonic acid morpholide (obtained from thiophene-2-carboxylic acid-S-sulfonic acid chloride and morpholine) there are obtained about 2.7 parts of the dyestuff of the formula The two dyestuffs last mentioned above also dye cotton from an olivegreen hydrosulfite vat fast wine red tints. Example 4 2.9 parts of thiophene-2-carboxylic acid-S-sulfonic acid isopropyl-methyl-amide (obtained, for example, from thiophene-Z-carboxylic acid-S-sulfonic acid chloride and isopropylamine followed by methylation at the nitrogen atom of the resulting thiophene-Z-carboxylic acid-S-sulfonic acid isopropylarnide by means of dimethylsulfate and a solution of sodium hydroxide) are stirred in 50 parts of dry nitrobenzene with 2 parts of thionyl chloride for /2 hour at 95 C., and then condensed, as described in Example 1, with 4.2 parts of 1-amino-4-benzoylamino-6 7-dichloranthraquinone. After working up there are obtained about 5.5 parts of the dyestufi of the formula CHa Cso:o

II I

It dyes cotton from an olive-green hydrosulfite vat fast pure violet-red tints.

Example 5 1.3 parts of thiophene-Z-carboxylic acid-S-sulfonic acid dimethylamide are stirred with 1.5 parts of thionyl chloride in 40 parts of dry nitrobenzene for /2 hour at 90 C., and then condensed with 2.25 parts of l-amino-4- (para chlorobenzoylamino) 6:7 dichloranthraquinone for 2 hours at 130 C. After cooling the mixture, the crystalline precipitate of the dyestutf is filtered off. washed with alcohol, and dried in vacuo at C.

There are obtained about 2.2 parts of the dyestutt of the formula Hfi-[CH /C Ila (I? HNOC--C C-SOr-N s cn. 01-

It dyes cotton from an olive-green hydrosulfite vat fast 3. The anthraquinone vat dyestuff of the formula violet tints. HC QH Example 6 0 1.4 parts of the dyestuif obtained as described in Ex- H ample 1 are vatted with 4 parts of sodium hydrosulfite and 8 parts by volume of sodium hydroxide solution of 30 per cent. strength in 200 parts of water at 4050 C.

A dyebath is prepared which contains in 2000 parts of water, 2 parts of sodium hydrosulfite and 4 parts by volume of sodium hydroxide solution of 30 per cent. strength, and the stock solution described above is added. 100

4. The anthraquinone vat dyestulf of the formula parts of cotton are then entered at 25 C., after minfi (fi[ /CH; utes 40 parts of sodium chloride are added and dyeing -oco C-SO N 1s contmued for one hour at 2530 C. The cotton 1s 15 ii 2- then squeezed, oxidized in the air, rinsed, acidified, again S CH3 rinsed and advantageously soaped at the boil. There is obtained a pure reddish violet dyeing having good properties of fastness. g I

What is claimed is: O

HN-OC- 1. An anthraquinone vat dyestufl of the formula HC-CH wherein one Y represents a chlorine atom and the other 0 L Y represents a bromine atom. I I 5. The anthraquinone vat dyestuif of the formula Y HC--CH CHr-OH:

H \S/ CH2C2 C1- HN-O C-R1 in which R1 stands for an aromatic radical selected from C1- the group consisting of the benzene and chlorobenzene radicals, X stands for a member selected from the group A Hlir-o o-Q consisting of the radicals 6. The anthraquinone vat dyestufi of the formula mHiM-i HCJCH CHr-CE:

H 0 HNO o-h ii-SOPN o ll l g S CH2C a CHPCHI Cl N/ 0 40 01 CHr-C: and I HNOC GHQ-CH1 7. The anthraquinone vat dyestuff of the formula -N OH:

\ HC-CH CHa CH3 wherein m and n each represent a whole number of at 1| the most 3, and Y stands for a member selected from 01 s the group consisting of Cl and Br.

2. An anthraquinone vat dyestufi of the formula 01 HC-CH mHm-H a It a HN--OCC o HN0CC SOr-N ll 5 References Cited in the file of this patent UNITED STATES PATENTS 01 2,505,253 Pitman et a1 Apr. 25, 1950 2,506,024 Jenny et a1. May 2, 1950 OTHER REFERENCES wherein m and n each represent a whole number of at and -5 P- the most 3. 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 